A composite article is provided which includes a fluoropolymer intimately bonded to a component including a substantially non-fluorinated thermoplastic having pendant phenolic groups in combination with a base. Increased adhesion is observed by a greater peel strength value between the fluoropolymer component and a non-fluorinated thermoplastic having pendant phenolic groups.

Fluoropolymers, or fluorine-containing polymers, are a commercially important class of materials. Fluoropolymers include, for example, uncrosslinked and crosslinked fluorocarbon elastomers and semi-crystalline or glassy fluorocarbon plastics. Fluorocarbon plastics (or fluoroplastics) are generally of high thermal stability and are particularly useful at high temperatures. They also exhibit extreme toughness and flexibility at very low temperatures. Many of these fluoroplastics are almost totally insoluble in a wide variety of solvents and, thus, are generally chemically resistant. Some have extremely low dielectric loss and high dielectric strength, and many have unique nonadhesive and low-friction properties. See, for example, F. W. Billmeyer, Textbook of Polymer Science, 3rd ed., pp. 398-403, John Wiley and Sons, New York (1984).
Fluorocarbon elastomers, particularly the copolymers of vinylidene fluoride with other ethylenically unsaturated halogenated monomers, such as hexafluoropropylene, have particular utility in high temperature applications, such as seals, gaskets, and linings. See, for example, R. A. Brullo, xe2x80x9cFluoroelastomer Rubber for Automotive Applications,xe2x80x9d Automotive Elastomer and Design, June 1985, xe2x80x9cFluoroelastomer Seal Up Automotive Future,xe2x80x9d Materials Engineering, October 1988, and W. M. Grootaert, et al., xe2x80x9cFluorocarbon Elastomers,xe2x80x9d Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 8, pp. 990-1005 (4th ed., John Wiley and Sons, 1993).
Fluoroplastics, particularly polychlorotrifluoroethylene, polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, and poly(vinylidene fluoride), have numerous electrical, mechanical, and chemical applications. Fluoroplastics are useful, for example, in wire coatings, electrical components, seals, solid and lined pipes, and piezoelectric detectors. See, for example, xe2x80x9cOrganic Fluorine Compounds,xe2x80x9d Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 11, pp., 20, 21, 32, 33, 40, 41, 50, 52, 62, 70, 71 (John Wiley and Sons, 1980).
In the automotive industry, for example, increased concern with evaporative fuel standards has led to the need for fuel system components that have improved barrier properties. This helps reduce the permeation of fuel vapors through automotive elements such as fuel filler lines, fuel supply lines, fuel tanks, and other elements of an automobile fuel system. Multi-layer tubing and other articles containing a fluorinated layer have been used in such automotive elements to provide a chemically resistant vapor barrier. Multi-layer articles are also useful in a number of other industries including, for example, the chemical processing and/or handling industries, and the electrical and electronics industries. Such multi-layer articles can include one or more other layers that can add strength, rigidity, or other mechanical properties.
Multi-layer compositions comprising a fluorinated polymer layer and a polyamide or polyolefin layer are known. See, for example, U.S. Pat. No. 4,933,090 (Krevor) which discloses laminate tubular articles that can include layers of fluorocarbon elastomers, and International Publication No. WO 93/14933 (LaCourt) which discloses a laminar film structure that includes a polyimide and a fluoropolymer.
To be useful, these multi-layer articles should not delaminate during use. That is, the bond strength between the layers of the multi-layer article should be sufficient to prevent the layers from separating. A variety of methods have been employed to increase the bond strength between a layer comprising a fluoropolymer and a layer comprising a substantially non-fluorinated polymer. For example, a layer of adhesive can be added between the two layers. However, the adhesive used must not limit the performance of the multi-layer article.
As an alternative to, or in addition to, adhesives, surface treatment of one or both of the layers has been used to increase the adhesive bond strength between the layers. For example, layers comprising a fluoropolymer have been treated with a charged gaseous atmosphere followed by application of a layer of thermoplastic polyamide.
In another approach, the adhesion between a substantially non-fluorinated polymer and a fluoropolymer, wherein the fluoropolymer is derived from vinylidene fluoride (VDF), and optionally hexafluoropropylene (HFP), has been found to increase upon exposure of the fluoropolymer to a primary or secondary amine compound. An example includes providing a layer comprising a fluoropolymer comprising interpolymerized units derived from vinylidene fluoride, a layer of a melt-processable, substantially non-fluorinated polymer, and a melt-processable aliphatic di- or polyamine of less than 1,000 molecular weight. See, for example, U.S. Pat. No. 5,658,670.
There are however certain circumstances where the production of such amine containing compounds or their subsequent use is problematic. What is needed is an alternative method for improving the adhesion between fluoropolymers and substantially non-fluorinated materials. This invention provides such a method.
In one aspect, the present invention provides a method of adhering or bonding a substantially non-fluorinated thermoplastic polymer to a fluoropolymer. In another aspect, the present invention provides a composite article comprising a substantially non-fluorinated thermoplastic polymer adhered to a fluoropolymer. In still another aspect, the present invention provides a multilayer article comprising a fluoropolymer adhered to a first surface of the substantially non-fluorinated thermoplastic polymer and a second polymer adhered to a second surface of the substantially non-fluorinated thermoplastic polymer. When the thermoplastic polymer layer comprises a functionalized polyolefin, (i.e., a polyolefin derived from the reaction of a functionalized olefin with a bisphenol), there is substantially no organo-onium present.
The method of the invention comprises the steps of
(a) providing (i) a substantially non-fluorinated thermoplastic polymer having one or more pendant phenolic groups, and optionally one or more primary or secondary pendant amine groups thereon, (ii) a base, and (iii) a fluoropolymer,
(b) at least partially reacting the phenolic group or groups with the base, to form a modified substantially non-fluorinated thermoplastic polymer,
(c) forming a composite article comprising the fluoropolymer in contact with a first surface of the modified thermoplastic polymer, and
(d) subjecting the composite article to pressure and/or temperature conditions adequate to bond the modified thermoplastic polymer to the fluoropolymer. When the thermoplastic polymer of step xe2x80x9caxe2x80x9d is an olefin derived from the reaction of a functionalized olefin with a bisphenol, there is substantially no organo-onium present during the process.
The composite article of the invention comprises a fluoropolymer layer bonded to a layer of the modified thermoplastic polymer. The composite article may further have a second substantially non-fluorinated thermoplastic polymer bonded to the modified thermoplastic polymer. The second thermoplastic polymer may be the same as, or different than, the modified thermoplastic polymer.
The embodiments of the invention are useful in providing a wide variety of shaped composite articles such as sheets and films, containers, hoses, tubes and the like. The articles so provided are especially useful wherever chemical resistance and/or barrier properties are necessary. Examples of specific uses for the composite structures of the invention include their use in rigid and flexible retroreflective sheets, adhesive articles such as adhesive tapes, paint replacement films, drag reduction films, fuel line and filler neck hoses, hydraulic fluid hoses, exhaust handling hoses, fuel tanks, and the like. The composite articles of the invention are also useful in chemical handling and processing applications, and as wire and cable coatings or jackets.
As used herein, a thermoplastic polymer, whether fluorinated or substantially non-fluorinated, means a polymer that is melt processable and has either (i) a glass transition temperature above ambient temperature (i.e., above 17xc2x0 C.) or (ii) a melt point and is semi-crystalline.
The fluoropolymers useful (also known as fluorinated polymers) include both vinylidene fluoride containing fluoropolymers and substantially non-vinylidene fluoride containing fluoropolymers and mixtures thereof. Additionally, the fluoropolymers used in the invention include both fluoroplastics (also known as fluorothermoplastics) and fluoroelastomers. Blends of various fluoropolymers may be employed in the invention if desired.
Fluoroplastics are distinguished from fluoroelastomers or fluororubbers by their properties. Fluoroplastic materials are melt-processable and have either a melt point and are semi-crystalline, or have a glass transition temperature above ambient temperature. In contrast, fluoroelastomers or fluororubbers are generally amorphous and usually do not exhibit a melt point. While some fluoroelastomers may be melt-processable, a curing step is typically used in making finished articles of fluoroelastomers. The curing step generally results in a material with substantially reduced melt-processability. The terms fluoroelastomer and fluororubber are generally used interchangeably. See, for example, American Society for Testing and Materials (ASTM) D 1566 for elastomer and rubber definitions.
Vinylidene Fluoride Containing Fluoropolymers
As used herein the term xe2x80x9cvinyridene fluoride containing fluoropolymersxe2x80x9d includes fluoropolymers derived from vinylidene fluoride (xe2x80x9cVF2xe2x80x9d or xe2x80x9cVDFxe2x80x9d) and fluoropolymers derived from other monomers which, when polymerized, form monomer sequences similar to polymerized vinylidene fluoride. Such monomers include ethylenically unsaturated monomers which, when incorporated into fluoropolymers, can produce a similar (including an identical) polymeric microstructure as the polymerized VDF. In general, the microstructure of a carbon bonded hydrogen atom between carbon bonded fluorine atoms creates a microstructure similar to polymerized VDF. The reactivity of a carbon bonded hydrogen is further enhanced when its carbon atom is adjacent to, or attached to a carbon atom possessing a carbon bonded xe2x80x94CF3 group (supplied by HFP or 2-hydropentafluoropropylene for instance) or another electron withdrawing group. Monomers suitable for forming such carbon-bonded-hydrogen reactive sites include, but are not limited to, VDF, 1-hydropentafluoropropene, 2-hydropentafluoropropene, and trifluoroethylene.
Preferably, these VDF-containing fluoropolymers are easily prone to dehydrofluorination and are also prone to a subsequent adhesion promoting reaction. The carbon-bonded-hydrogen sites produced upon copolymerization of these monomers, including VDF, can be pre-dehydrofluorinated to form double bonds within the backbone of the fluoropolymer. While not wishing to be bound by any particular theory, it is believed that preformation of these double bonds may accelerate the adhesion promoting reaction. This dehydrofluorination reaction may also be produced in situ, e.g., during processing. This in situ dehydrofluorination reaction may be aided by the use of an appropriate catalyst, preferably of the type discussed below. Such VDF-containing fluoropolymers comprise at least 3% by weight of interpolymerized units derived from VDF or other monomers with similar microstructure when polymerized. These VDF-containing fluoropolymers may be homopolymers or copolymers with other ethylenically unsaturated monomers. More preferably, the VDF-containing fluoropolymer is formed from (i) a fluorine-containing monomer selected from the group of trifluoroethylene, 1-hydropentafluoropropylene, 2-hydropentafluoropropylene, mixtures thereof, and optionally (ii) at least one monomer copolymerizable therewith. In one preferred embodiment, the VDF-containing fluoropolymer comprises a hexafluoropropylene-vinylidene fluoride polymer.
Such VDF-containing fluoropolymers (homopolymers, copolymers, terpolymers, etc.) can be made by well-known conventional means, for example by, free-radical polymerization of VDF with or without other ethylenically unsaturated monomers. The preparation of colloidal, aqueous dispersions of such polymers and copolymers is described, for example, in U.S. Pat. No. 4,335,238 (Moore et al.). Customary processes for making such fluoropolymers can include copolymerizing fluorinated olefins in aqueous, colloidal dispersions, which is carried out in the presence of water-soluble initiators which produce free radicals, such as, for example, ammonium or alkali metal persulfates or alkali metal permanganates, and in the presence of emulsifiers, such as, in particular, the ammonium or alkali metal salts of perfluorooctanoic acid.
The VDF-containing fluoropolymers useful in this invention can optionally include other useful fluorine-containing monomers such as hexafluoropropene (HFP), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), 2-chloropentafluoro-propene, a fluorinated vinyl ether, including a perfluoroalkyl vinyl ether such as CF3OCFxe2x95x90CF2 or CF3 CF2 CF2OCFxe2x95x90CF2. Certain fluorine-containing di-olefins are also useful, such as, perfluorodiallyether and perfluoro-1,3-butadiene.
The VDF-containing fluoropolymers useful in this invention may also comprise interpolymerized units derived from fluorine-free, unsaturated olefin comonomers, e.g., ethylene, propylene or butadiene. Preferably, at least 50% by weight of all monomers in a polymerizable mixture are fluorine-containing. The VDF-containing fluorine-containing monomer may also be copolymerized with iodine- or bromine-containing unsaturated olefin monomer. These monomers, sometimes referred to as cure-site monomers, are useful to prepare a peroxide curable polymer. Suitable cure-site monomers include terminally unsaturated monoolefins of 2 to 4 carbon atoms such as bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, and 4-bromo-3,3,4,4-tetrafluoro-1-butene.
Useful commercially available VDF-containing fluoropolymer materials include, for example, THV 200, THV 400, THV 500G fluoropolymer (available from Dyneon LLC, St. Paul, Minn.), KYNAR 740 fluoropolymer (available from Atochem North America, Philadelphia, Pa.), HYLAR 700 (available from Ausimont USA, Inc., Morristown, N.J.), and FLUOREL FC-2178 (available from Dyneon LLC).
Substantially Non-vinylidene Fluoride Containing Fluoropolymers
These fluoropolymers typically do not contain VDF monomer (or any other similar monomer) at a level such that, when polymerized, produces a microstructure which is similar to polymerized VDF. Hence, these fluoropolymers are referred to herein as xe2x80x9csubstantially non-vinylidene fluoride (non-VDF) containing fluoropolymers.xe2x80x9d By xe2x80x9csubstantially non-VDF containing,xe2x80x9d it is meant that the fluoropolymer preferably is substantially free from interpolymerized units derived from VDF monomer, or other monomers which provide a microstructure similar to that described above. These fluoropolymers comprise less than 3%, preferably less than 1% by weight of interpolymerized units derived from VDF or other monomers which produce a microstructure similar to that described above.
An example of a useful non-VF2 fluoropolymer comprises a terpolymer of ethylene, hexafluoropropylene and tetrafluoroethylene. Such terpolymers preferably have a melting point of less than 168xc2x0 C. A preferred terpolymer of these three monomers has an ethylene content of at least 11% and a hexafluoropropylene content of at least 22%.
Examples of non-VF2 containing fluoropolymers include Dyneon ETFE 6235, Dyneon E-14659 and E-14660, Dyneon PFA 6502N and 6515N, Dyneon FEP 6101 and 6107, Hostaflon PTFE TF1620 and Hostaflon TFM1600 and Aflas FA-100S and FA-150P (all available from Dyneon LLC). Other examples include Halar ECTFE 300 and 500 (available from Ausimont USA Inc., Morristown, N.J.).
In the case of many of these non-VF2 containing fluoropolymers, it may be necessary to treat the surface, or bulk, of the fluoropolymer to enhance or promote the adhesion with the phenolic-containing component. Treatment may be accomplished with any of several methods known in the industry, such as: contact with a solution of elemental sodium, corona treatment from an electrical discharge in air or another atmosphere, or by flame treatment. These treatments are believed to induce double bonds or other chemical functionality along the backbone or surface of the fluoropolymer thereby allowing a site for adhesion with the phenolic containing component. The above mentioned treatments can also be applied to VF2 containing class of polymers.
Blends of fluoropolymers from the VF2 and non-VF2 containing classes may also be employed in the invention.
Substantially Non-Fluorinated Polymers
Useful substantially non-fluorinated materials can include any of a number of well known, substantially non-fluorinated polymers. As used herein the term xe2x80x9csubstantially non-fluorinatedxe2x80x9d refers to polymers and polymeric materials having fewer than 10 mole percent of carbon-bonded fluorine atoms. Preferably, the substantially non-fluorinated polymer has fewer than 2 mole percent of carbon-bonded fluorine atoms, and more preferably fewer than 1 mole percent of carbon-bonded fluorine atoms. A particularly useful subclass of substantially non-fluorinated fluoropolymers are those that have one or more pendant primary or secondary amine groups.
Examples of classes of substantially non-fluorinated polymers useful in the invention include thermoplastic polymers such as polyamides, polyimides, polyurethanes, polyolefins, polystyrenes, polyesters, polycarbonates, polyketones, polyureas, polyacrylates and polymethacrylates. The particular substantially non-fluorinated polymer selected will depend upon the application or desired properties, such as chemical and/or flame resistance, of the composite article according to the invention.
Polyamides useful as the substantially non-fluorinated polymer are generally commercially available. For example, polyamides such as any of the well-known nylons are available from a number of sources. Particularly preferred polyamides are nylon-6, nylon-6,6, nylon-11, or nylon-12. It should be noted that the selection of a particular polyamide material should be based upon the physical requirements of the particular application for the resulting article. For example, nylon-6 and nylon-6,6 offer higher heat resistant properties than nylon-11 or nylon-12, whereas nylon-11 and nylon-12 offer better chemical resistant properties. In addition to those polyamide materials, other nylon materials such as nylon-6,12, nylon-6,9, nylon-4, nylon-4,2, nylon-4,6, nylon-7, and nylon-8 may also be used. Ring containing polyamides, e.g., nylon-6,T and nylon-6,1, may also be used. Polyether containing polyamides, such as PEBAX polyamides (Atochem North America, Philadelphia, Pa.), may also be used. Other useful polyamides include a zinc chloride resistant nylon-6 based material available as NYLTECH 7551 (Nyltech North America, Manchester, N.H.) and a polyamide having an excess of amine groups such as GRILAMID L20HV1 (EMS American Grilon, Sumter, S.C.).
Useful polyurethane polymers include aliphatic, cycloaliphatic, aromatic, and polycyclic polyurethanes. These polyurethanes are typically produced by reaction of a polyfunctional isocyanate with a polyol according to well known reaction mechanisms. Useful diisocyanates for employment in the production of a polyurethane include dicyclohexylmethane-4,4xe2x80x2-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexyl diisocyanate, and diphenylmethane diisocyanate. Combinations of one or more polyfunctional isocyanates may also be used. Useful polyols include polypentyleneadipate glycol, polyetramethylene ether glycol, polyethylene glycol, polycaprolactone diol, poly-1,2-butylene oxide glycol, and combinations thereof Chain extenders, such as butanediol or hexanediol, may also optionally be used in the reaction. Commercially available urethane polymers useful in the present invention include: PN-04 or 3429 from Morton International, Inc., Seabrook, N.H., and X-4107 from B.F. Goodrich Company, Cleveland, Ohio.
The polyolefin polymers useful as the substantially non-fluorinated polymer are generally homopolymers or copolymers of ethylene, propylene, acrylic monomers, or other ethylenically unsaturated monomers, for example, vinyl acetate and higher alpha-olefins. Such polymers and copolymers can be prepared by conventional free-radical polymerization or catalysis of such ethylenically unsaturated monomers. The degree of crystallinity of the hydrocarbon polymer or copolymer can vary. The polymer may, for example, be a semi-crystalline high density polyethylene or may be an elastomeric copolymer of ethylene and propylene. Carboxyl, anhydride, or imide functionalities may be incorporated into the hydrocarbon polymer within the present invention, by polymerizing or copolymerizing functional monomers, for example, acrylic acid or maleic anhydride, or by modifying a polymer after polymerization, for example, by grafting, by oxidation or by forming ionomers. These include, for example, acid modified ethylene vinyl acetates, acid modified ethylene acrylates, anhydride modified ethylene acrylates, anhydride modified ethylene vinyl acetates, anhydride modified polyethylenes, and anhydride modified polypropylenes. The carboxyl, anhydride, or imide functional polymers useful as the hydrocarbon polymer are generally commercially available. For example, anhydride modified polyethylenes are commercially available from DuPont, Wilmington, Del., under the trade designation BYNEL coextrudable adhesive resins.
Polyacrylates and polymethacrylates useful as the substantially non-fluorinated polymer include, for example, polymers of acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methylacrylic acid, methyl methacrylate, and ethyl acrylate, to name a few. As mentioned above, other useful substantially non-fluorinated polymers include polyesters, polycarbonates, polyketones, and polyureas. These materials are generally commercially available, for example, SELAR polyester (DuPont, Wilmington, Del.), LEXAN polycarbonate (General Electric, Pittsfield, Mass.), KADEL polyketone (Amoco, Chicago, Ill.), and SPECTRIM polyurea (Dow Chemical, Midland, Mich.).
Substantially non-fluorinated elastomeric materials useful in the current invention include acrylonitrile butadiene (NBR), butadiene rubber, chlorinated and chloro-sulfonated polyethylene, chloroprene, EPM, EPDM, epichlorihydrin (ECO), isobutylene isoprene, isoprene, polysulfide, polyurethane, silicone, PVC-NBR, styrene butadiene, and vinyl acetate ethylene. Examples of these compounds include Nipol 1052 NBR (Zeon, Lousville, Ky.), Hydrin 2000 ECO (Zeon, Louisville, Ky.), Hypalon 48 (Dupont, Wilmington Del.), and Nordel 2760P EPDM (Dupont, Wilimington Del.).
Substantially Non-Fluorinated Thermoplastic Polymer having Pendant Phenolic Groups
Useful substantially non-fluorinated thermoplastics having at least one pendant phenolic group, include any of the substantially non-fluorinated thermoplastic polymers described above so long as a pendant phenolic group is present. As noted, these thermoplastic polymers may also have at least one pendant primary or secondary amine group, the pendant phenolic group may be a substituted or unsubstituted phenolic group. The polymer may contain both pendant substituted and unsubstituted phenolic groups. The phenolic group or groups may be incorporated into the substantially non-fluorinated polymer by copolymerization with a monomer containing a substituted or unsubstituted phenolic group. Alternatively, a phenolic containing compound may be mixed and reacted with a substantially non-fluorinated polymeric material. Similarly, the corresponding base may be added during or subsequent to the polymerization of the substantially non-fluorinated thermoplastic.
A particularly useful substituted phenolic salt compound is commercially available under the trade designation P-152, available from Mitsui Chemicals (Nashville, Tenn.). This material is said to be phenolic resin salts of 1,8diazabicyclo[5,4,0]undec-7-ene. For example, the P-152 may be mixed and reacted with a maleic anhydride functionalized polyolefin to produce the pendant phenoxide containing hydrocarbon polymer.
Other materials which may be modified with the addition of pendant phenoxide groups include polyamides, polyimides, polyurethanes, polystyrenes, polyesters, polycarbonates, polyketones, and polyureas. These materials are generally commercially available, for example, NYLTECH 755 polyamide from Nyltech North America (Manchester, N.H.), GRILAMID L20HV1 polyamide from EMS American Grilon (Sumter, S.C.), SELAR polyester from DuPont (Wilmington, Del.), LEXAN polycarbonate (General Electric, Pittsfield, Mass.), KADEL polyketone (Amoco, Chicago, Ill.), and SPECTRIM polyurea (Dow Chemical, Midland, Mich.).
The pendant phenolic groups may include either end-groups or pendant side chain groups of any polynuclear aromatic alcohol. These include pendant groups of unsubstituted and substituted phenolics, phenolic resins, resorcinols, hydroquinones, napthols, bis-phenols, and salts thereof, to name a few.
Bases
Bases can be inorganic or organic compounds. Organic bases include tertiary amines and amidine compounds, alkoxide salts, sodium stearate, magnesium oxalate, and benzotriazoate. Inorganic bases include magnesium oxide, lead oxide, calcium oxide, calcium hydroxide, sodium hydroxide, magnesium hydroxide, potassium hydroxide, lithium hydroxide, dibasic lead phosphite, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, etc.
Representative classes of useful amine compounds include aliphatic, aryl and amidine amine compounds. Examples of these include 4-dimethyl amino pyridine, triisooctyl amine, 1,8-diazobicyclo(2,2,2)-octane, 1,5-diazobicyclo[4.3.0] non-5-ene, and 1,8-diazobicyclo[5.4.0]undec-7-ene, imidazole, benzotriazole, to name a few.
A useful class of amine compounds can be represented by the following formula:
where:
R1, R2 are independently selected from hydrogen, substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and
R3 is selected from substituted or unsubstituted alkylene, cycloalkylene, arylene, aralkylene, and alkarylene groups; n is a number from 0 to about 100. Preferably R1 and R2 are selected from substituted and unsubstituted alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups.
Organo-Onium Compounds
Organo-onium compounds may be employed in the practice of some aspects of the invention. However, if the substantially non-fluorinated thermoplastic polymer having a pendant phenolic group is an olefin derived from the reaction of a functionalized polyolefin and a bisphenol, no organo-onium should be employed. However, when the thermoplastic polymer is not an olefin, organo-onium compounds may be used.
Organo-oniums are known, are described in the art and contain at least one heteroatom (i.e., a non-carbon atom such as N, P, S, O) bonded to organic or inorganic moieties. See, for example, U.S. Pat. No. 4,882,390 (Grootaert et al.); U.S. Pat. No. 3,655,727 (Patel et al.); U.S. Pat. No. 3,712,877 (Patel et al.); U.S. Pat. No. 3,857,807 (Kometani): U.S. Pat. No. 3,686,143 (Bowman); U.S. Pat. No. 3,933,732 (Schmiegel); U.S. Pat. No. 3,876,654 (Pattison); U.S. Pat. No. 4,233,421 (Worm); U.S. Pat. No. 4,259,463 (Moggi et al.); U.S. Pat. No. 4,673,715 (Caywood): U.S. Pat. No. 4,833,212 (Yamada et al.); U.S. Pat. No. 4,748,208 (Kasahara et al.); U.S. Pat. No. 4,501,858 (Moggi); U.S. Pat. No. 4,882,390; and also see West, A. C. and Holcomb, A. G. xe2x80x9cFluorinated Elastomersxe2x80x9d, Kirk-Othmer; Encyclopedia of Chemical Technology, Vol. 8, 3rd Ed., John Wiley and Sons, Inc., pp. 500-515 (1979). Mixtures of organo-onium compounds are also useful in this invention.
Preferably, the organo-onium compounds include quaternary organo-onium compounds (such as those selected from the group consisting of ammonium, arsonium, phosphonium, stibonium, amino-phosphonium, phosphorane and immium compounds) and sulfonium compounds. Many of such compounds are described in U.S. Pat. No. 4,882,390 (Grootaert et al.).
Representative organo-onium compounds useful in this invention include: tetrabutylammonium chloride, tetrabutylammonium bromide, tetrahexylammonium chloride, tetraheptylammonium chloride, triphenylben-zylphosphonium chloride, tetrapentylammonium chloride, tributylallylphosphonium chloride, tributylbenzylphosphonium chloride, dibutyldipbenylphosphonium chloride, tetrabutylphosphonium chloride and tributyl(2-metboxy)propylphosphonium chloride, phenyltrimethylammonium chloride, tetrapropylammonium bromide, tetraheptylammonium bromide, tetramethylphosphonium chloride, tetramethylammonium chloride, tetraphenylphosphonium chloride, tetraphenylarsonium chloride, tetraphenylstibonium chloride, 8-benzyl-1, 8-diazobicyclo[5.4.0]7-undecenium chloride, benzyltris(dimethylamino) phosphonium chloride, bis(benzyldiphenylphosphine) iminium chloride compounds and mixtures thereof
Optional Additives
The composite articles in accordance with the invention may also include optional additives, such as those typically used in other thermoplastic applications. The optional additives are preferably selected from the group of a pigment, a plasticizer, a tackifier, a filler, electrically conductive materials (such as those described in U.S. Pat. No. 5,552,199), electrically insulative materials, a stabilizer, an antioxidant, a lubricant, a processing aid, an impact modifier, a viscosity modifier, and mixtures thereof
Composite Article Formation
Methods known in the polymer art can be used to produce a composite article, such as a bonded multi-layer article, wherein the fluoropolymer component is in substantial, preferably intimate, contact with the substantially non-fluorinated thermoplastic material having pendant substituted and/or unsubstituted phenolic groups and base. For instance, the fluoropolymer component and the substantially non-fluorinated thermoplastic material and base can be formed by known methods into thin films or thicker sheets. These films or sheets can be laminated together under heat and/or pressure to form a bonded multi-layer article. Alternatively, the fluoropolymer component and the substantially non-fluorinated polymer having pendant substituted and/or unsubstituted phenolic groups and base can be simultaneously co-extruded into a multi-layer article.
In addition, all of these methods can be used to apply additional polymeric components or layers either before, during, or after the formation of the fluoropolymer component in contact with the component including the substantially non-fluorinated polymer having pendant phenolic groups.
Conditions by which two or more components are brought together (e.g., sequential extrusion, co-extrusion or lamination, to name a few) may be sufficient to provide adequate adhesion between the components. However, it may be desirable to further treat the resulting composite article with, for example, heat and/or pressure to improve adhesion. One way to supply additional heat, for example, is to slow the rate of cooling after extrusion of the components. Also, additional heat or energy can be added during or after extrusion or lamination processes, wherein the temperatures may be higher than that required for merely processing the components. Further, the complete composite article may be held at an elevated temperature and/or pressure for an extended period of time, such as in an oven, an autoclave, a heated liquid bath and the like. A combination of these methods can also be used.

Composite articles including a fluoropolymer


A sales system having a plurality of wearable portable terminals each having an optical code reader and a wireless transceiver, a plurality of stationary terminals each having a wireless transceiver and a central database having information relating to goods to be sold by the system. A wireless network interconnects the portable terminals, stationary terminals and the central database.

The present invention relates to a sales system, and in particular to an escorted shopper system.
Sales systems which incorporate portable terminals that are used by the shoppers to record purchases are known.
It has become apparent in retail stores that customers desire improved service, but it is difficult to provide with inexperienced employees and insufficient inventory information available to employees on the sales floor. Moreover, existing systems require the sales person to leave the customer to find out information that the customer seeks, and customers perceive this as poor service.
The main object of the present invention is to improve the known sales systems and to provide an escorted shopper system wherein the salesperson can accompany the customer on the sales floor even when information is being gathered for the customer.
Another object of the present invention is an improved wearable portable terminal which can be used in an escorted shopper system.
The escorted shopper system according to the present invention includes a plurality of wearable, portable terminals primarily for use by employees of a retail store and a plurality of stationary terminals. A central database has information relating to the goods to be sold in the store and a wireless network interconnects the portable terminals and the stationary terminals with the central database and each other. The present invention also relates to an improved wearable, portable terminal which can be used in the escorted shopper system according to the present invention.
The escorted shopper system empowers any employee in a retail setting to provide a more personal shopping experience by enabling the employee to escort the customer through every aspect of the shopping trip. Beginning as early as the point of entry in the store and continuing through the points of decision and ending at the point of sale, the employee is able to assist with anything, as well as complete the sale, without ever having to leave the customer. The system according to the present invention provides the platform that enables any store employee to completely follow through with any customer allowing a totally customized shopping experience.
The escorted shopper system in accordance with the invention provides all the necessary tools for dealing with a customer, including sales assistance, communication, transactional capabilities and access to inventory. The present invention consolidates all of these functions into one wearable, portable terminal that can be used by employees as part of the shopper system.
The escorted shopper system according to the present invention can operate in sales mode, inventory mode and transaction mode.
In the sales mode, the escorted shopper system serves as an on the spot resource for the employee, feeding the employee product, policy and/or customer service information as needed. Furthermore, the portable terminal acts as a communication link among employees, ensuring immediate sales or security assistance. In both cases, it eliminates the need for the employee to go to other areas of the store for assistance and leave the customer waiting. The portable terminal and the system provide an open platform for information dispersal and communication among employees, empowering the employees to more effectively and knowledgeably interface with customers. The customer is able to get a running total of chosen items before purchase, have any questions relating to those purchases answered, even by inexperienced employees, and enable the customer to find exactly what the customer is looking for.
In the inventory mode, the portable terminal and system allows an employee remote access to inventory databases, local or otherwise, as well as the ability to contribute to those databases in real time. The employee can actively update the database to insure accuracy. The system can act as a tracking system, not only of the in-store merchandise, but availability anywhere and creates the potential to close sales on merchandise outside the store""s premises. Accurate tracking of inventory is extremely important for a retailer and up to the minute data integrity means never having to look in the stock for desired items, since this knowledge is at the employee""s fingertips.
In the transactional mode, the terminal and system allows a customer to make a cashless transaction or multiple transactions anywhere in the store. This eliminates the need to wait in line and allows the processing of returns with credit given to an account. The portable units within the system act as a mobile point of sale, allowing an employee to conclude the transaction anywhere in the store.
In accordance with the invention, the escorted shopper system has two main components, the wearable, portable terminal which is worn by all employees and a series of stationary terminals which can be moved to different locations in a store, but are not portable. Both operate within the wireless network setup within the store. The wearable, portable terminal acts as a thin client utilizing wireless transceivers, preferably RF, while the stationary terminals act as an access point for information dissemination. Within the wireless network, employees are enabled to access and contribute to multiple databases remotely. The stationary terminals serve the employee and the customer by being both a mobile point of sale, as well as an informational kiosk and a self-service scanner.
The wearable, portable terminal, because it is connected to the network, has a display which serves as a window into the multiple databases accessible by the network. The employee is always connected to the store""s computer and to other employees. The network in accordance with the present invention allows for voice over IP and therefore sales and security assistance can be obtained in real time and independent of physical proximity.
The wearable, portable terminals also preferably have a small laser scanner integrated therein to create the opportunity for cataloging merchandise real time anywhere in the store. A simple scan of the bar code on a tag can reconcile shrinkage and misplaced merchandise, as well as differentiate between sale and regularly priced items.
For transactional capabilities, the portable terminal preferably has a magnetic stripe reader embedded into the housing to allow credit cards to be swiped through the device. Carrying out a cashless transaction can now occur anywhere in the store. The signature and printing of a receipt will be carried out at the stationary terminals.
The stationary terminals can be located in multiple places throughout the store and, although normally stationary, are movable into different configurations within the store.
The stationary terminals can, in a compact configuration, contain only a display, a scanner, a printer, a magnetic stripe reader and peripheral fixtures, such as hanger and bag racks. After the customer""s card has been swiped on the sales floor, the information can be relayed to the closest stationary terminal where the receipt is printed. Signature and bagging can take place at the stationary terminal as well. The terminals can also be used to present advertisements or as informational sources for customers, inviting the customers to use them for obtaining information about items within the store. The scanner associated with the stationary terminal, which is preferably an omni-directional scanner, would allow the customers to get a running total of chosen items at the terminal if they so choose. The stationary terminals are preferably not intended to replace point of sale terminals, but in addition thereto.
In one example of the use of the present invention, a sales associate for the retail store arrives at work and punches in an employee identification number into the network and is issued a portable, wearable terminal that is now connected to the storewide wireless network. The device automatically informs the employee of who is working with him and what positions they are assigned to. The employee can also use the system to find out for himself what floor positions are not already filled, so he can take one of those positions. The employee can also find out from the system that two employees are actively updating inventory and three employees are actively tied to the cash wrap and only two employees are actively working the sales floor. Therefore, the employee can toggle his device to the sales mode, since the inventory and transaction functions are already covered.
The employee, while waiting for customers, can start folding and updating inventory by scanning bar codes on the goods. In this way, the employee actively contributes to a real time inventory database that will determine week to week, day to day, and even hour to hour which merchandise should be pushed by the employees.
While this employee is busy in the back of the store, customers can be greeted at the entrance of the store by a second employee who is to provide a point of contact for customers. She can alert the first employee to the customer by paging using graphics, vibration or sound. Since the network allows for voice over IP, the wearable, portable terminal allows the units to act as open channel radios or two way telephones. Thus, the employee can respond to the page and attend to the customer.
When the customer tells him what she is looking for, he can check on his portable terminal if that item, and in the particular size, is in stock on the sales floor or in the back of the store. If the employee finds out that the item is in a location that he cannot access, he can page another employee who access to that location to obtain the item for the customer.
The employee can thereafter complete a purchase by checking out the customer using the portable terminal. The sales associate can swipe the customer""s credit card on the magnetic stripe reader on the portable unit. The portable unit can alert the sales associate that the customer has an unused store credit from a previous return, and the sales associate can ask the customer if she would like to use the credit now. The receipt will be printed at the nearest stationary terminal location where the sales associate can bag the merchandise and allow the customer to sign the receipt.
As a result of the unique shape of the portable terminal in accordance with a preferred embodiment of the present invention, the device can be worn on the wrist like a watch, it can be clipped onto a belt or it can be tethered on a chain or the like around the neck. This way an employee has the benefit of hands free operation while still being able to access information. The device can also be held in a hand with the device wrapping around the middle finger without hindering its movement. This way the employee can use his or her hand even while holding the portable terminal. The housing of the terminal is preferably composed of a thermoplastic elastimer which is tactile enough to keep the product from slipping off one""s finger. Moreover, in a preferred embodiment of the present invention the scan button is positioned directly where the corresponding knuckle on the index finger rests when the fingers are compressed, making it intuitive and comfortable motion for scanning.
In a preferred embodiment of the present invention, the portable terminal is smaller than a credit card, however, the clam shell-like fold over form factor enables the terminal to wrap around the card and read it by clicking the two halves together and sliding the magnetic stripe relative to the reader which is located near a flat surface on the inner surface of the terminal. With one hand holding the card stationary, the other is used to run the device along the bottom of the card where the reader is already aligned with the stripe.
The clam shell like fold over configuration lends itself to be worn like a pager, clipped onto a pocket or a belt. When snapped together, the band forms a closed loop making a perfect place to put a tether for wearing around the neck or through a key ring.
One of the advantages of the shopper system according to the present invention is the elimination of long lines at the cash wrap or point of sale.
These and other objects and advantages of the present invention are achieved in accordance with the present invention by a shopper system comprising a plurality of wearable, portable terminals each having one or more of various types of data acquisition devices such as an optical code reader such as a laser scanner or an imager, an RFID device and a magnetic stripe reader and a wireless transceiver, a plurality of stationary terminals each having a wireless transceiver, a central database having information relating to goods to be sold by the system and wireless network interconnecting the portable terminals, stationary terminals and the central database. In a particularly advantageous preferred embodiment of the present invention, each of the wearable terminals is a c-shaped or clam shell shaped housing configured to be worn on a wrist or clipped onto a pocket or belt.


Ingestable products for lowering blood total cholesterol, including isoflavone, vegetable protein such as soy protein and phytosterol. The combination of phytosterol with soy protein (which includes isoflavone) is superior to the individual components alone in improving plasma lipid profiles. Preferably the products are food products. The invention is also a method for lowering plasma cholesterol in animals, preferably humans, by feeding compositions having plasma cholesterol-lowering, synergistically effective amounts of isoflavone, soy protein and phytosterol.

The following abbreviations are used in the course of the present application:
Despite considerable research efforts over the years, coronary heart disease (CHD) remains a formidable threat to the health of people in many countries throughout the world. Among factors considered to be of predictive value concerning the risk of CHD, an important traditional one has been blood total cholesterol (TC) levels, while in recent years the relative amounts of HDL cholesterol and LDL cholesterol have been linked to risk of CHD. High ratios of HDL to LDL are now generally considered as an indicator of salutary cardiac status.
Phytosterols, i.e., plant sterols, are well documented to have a hypocholesterolemic effect. Phytosterols inhibit intestinal cholesterol absorption, thereby lowering blood total and low-density lipoprotein (LDL) cholesterol concentrations. In human studies, phytosterols have been shown to reduce blood cholesterol concentration by an average of 10%. Moghadasian M H, Frohlich J J, xe2x80x9cEffects of dietary phytosterols on cholesterol metabolism and atherosclerosis: clinical and experimental evidence.xe2x80x9d Am J Med 1999;107:588-594.
Soy protein is among a number of other food ingredients which have been well documented to have a hypocholesterolemic effect. Dietary intake of soy protein has been associated with reduced blood cholesterol concentrations and a lower incidence of coronary heart disease based on a number of the reports obtained from animal, (Potter S M. xe2x80x9cOverview of proposed mechanisms for the hypocholesterolemic effect of soy.xe2x80x9d J Nutr 1995;125:606S-611S), human (Cassidy A, Bingham S, Setchell K D. xe2x80x9cBiological effects of a diet of soy protein rich in isoflavones on the menstrual cycle of premenopausal women,xe2x80x9d Am J Clin Nutr 1994;60:333-340; Teixeira S R, Potter S M, Weigel R, Hannum S, Erdman J W J, Hasler C M. xe2x80x9cEffects of feeding 4 levels of soy protein for 3 and 6 wk on blood lipids and apolipoproteins in moderately hypercholesterolemic men,xe2x80x9d Am J Clin Nutr 2000;71:1077-1084,) and epidemiological (Hollman P C, Katan M B. xe2x80x9cDietary flavonoids: intake, health effects and bioavailability,xe2x80x9d Food Chem Toxicol 1999;37:937-942) studies.
The mechanisms by which soy protein exerts its hypocholesterolemic effect may be different from that of phytosterols. It is generally assumed that the cholesterol lowering effects of soy protein are mediated through an increased plasma cholesterol clearance and/or an increased bile acid formation and excretion (Cassidy A, Bingham S, Setchell K D, xe2x80x9cBiological effects of a diet of soy protein rich in isoflavones on the menstrual cycle of premenopausal women,xe2x80x9d Am J Clin Nutr 1994;60:333-340; Lichtenstein A H. xe2x80x9cSoy protein, isoflavones and cardiovascular disease risk,xe2x80x9d J Nutr 1998;128:1589-1592; Baum J A, Teng H, Erdman J W J, et al. xe2x80x9cLong-term intake of soy protein improves blood lipid profiles and increases mononuclear cell low-density-lipoprotein receptor messenger RNA in hypercholesterolemic, postmenopausal women,xe2x80x9d Am J Clin Nutr 1998;68:545-551).
Although the cholesterol lowering effect of soy protein is well documented, the component(s) responsible for this effect in soy protein are still not identified. Soy protein is a rich source of isoflavones. While several studies appear to have demonstrated that the isoflavones in the soy protein may be the cause of the cholesterol lowering effect, (Merz-Demlow B E, Duncan A M, Wangen K E, et al. xe2x80x9cSoy isoflavones improve plasma lipids in normocholesterolemic, premenopausal women,xe2x80x9d Am J Clin Nutr 2000;71:1462-1469; Anthony M S, Clarkson T B, Williams J K, xe2x80x9cEffects of soy isoflavones on atherosclerosis: potential mechanisms, Am J Clin Nutr 1998;68:1390S-1393S; Ni W, Yoshida S, Tsuda Y, Nagao K, Sato M, Imaizumi K., xe2x80x9cEthanol-extracted soy protein isolate results in elevation of serum cholesterol in exogenously hypercholesterolemic rats,xe2x80x9d Lipids 1999;34:713-716; Crouse J R, Morgan T, Terry J G, Ellis J, Vitolins M, Burke G L, xe2x80x9cA randomized trial comparing the effect of casein with that of soy protein containing varying amounts of isoflavones on plasma concentrations of lipids and lipoproteins,xe2x80x9d Arch Intern Med 1999;159:2070-2076), other studies appear to have shown that the soy protein itself (including soy amino-acids or peptides) or the protein-associated substances other than isoflavones exhibited a cholesterol lowering activity (Greaves K A, Wilson M D, Rudel L L, Williams J K, Wagner J D. xe2x80x9cConsumption of soy protein reduces cholesterol absorption compared to casein protein alone or supplemented with an isoflavone extract or conjugated equine estrogen in ovariectomized cynomolgus monkeys,xe2x80x9d J Nutr 2000;130:820-826).
A hypotriglyceridemic effect of soy protein in human subjects was noted in a meta-analysis by Anderson J W, Johnstone B M, Cook-Newell M E in xe2x80x9cMeta-analysis of the effects of soy protein intake on serum lipids,xe2x80x9d N.Engl.J Med 1995;333:276-282.
Other ingestable materials which have been suggested in scientific literature or the press as causing improvement in cholesterol status or potential cholesterol improvement effects include: statins, niacin, inositol hexaniacinate, Vitamin E, tocotrienols, vitamin C, pantethine, quercetin, chromium, calcium, magnesium, L-carnitine, soy, chondroitin sulfate, lecithin, chitosan, royal jelly and copper. Despite the many agents which have been mentioned thus far in the scientific and popular literature as having potential cholesterol improving benefits in animals and humans, there is still a serious need for many individuals to improve further their cholesterol status, preferably without resorting to pharmaceuticals.
The problem of elevated cholesterol levels has received considerable attention in the patent literature, as well.
Potter et al., U.S. Pat. No. 5,855,892 discloses that daidzein and its metabolites, o-desmethylangolensin and dihydrodaidzein are useful for altering the concentration of cholesterol constituents in the blood of a human by increasing the concentration of high density lipoprotein cholesterol and decreasing the concentration of low density lipoprotein cholesterol. Potter et al. also report that vegetable protein materials, particularly soy protein materials, are known to reduce total cholesterol and LDL-cholesterol levels in the blood of animals.
Phytoestrogens in the soy protein are said to be recognized as a potentially significant factor in the hypocholesteremic effects of soy protein, and estrogen itself is said to be determined to be a significant cardio protective factor. In their background discussion, Potter et al. report that recent studies have determined that isoflavones lower blood concentrations of total cholesterol and LDL cholesterol in animals and thereby inhibit or slow the development of atherosclerosis, but that the effect of these isoflavones on blood cholesterol level in humans has been less clear.
The Potter et al. invention is directed to a method of altering the concentration of the cholesterol constituents in the blood of a human to reduce the risk of atheroschlerosis and vascular disease by administering a material containing daidzein to a human in an amount effective to increase the concentration of HDL cholesterol and to decrease the concentration of LDL cholesterol in the blood of a human. In one embodiment, daidzein is administered in a human in a soy protein material dietary supplement. Dietary supplements incorporating daidzein can be prepared by adding daidzein to a food which is said to include almost all foods, such as beverages, including nutritional beverages, frozen desserts such as ice cream, ice milk, low fat frozen desserts and non-dairy frozen desserts, soups, salad dressings and dips and spreads such as mayonnaise and chip dips. Acceptable and effective daily doses are said to be from about 10 to about 1,000 milligrams per day, more typically from about 30 to about 500 milligrams per day and most preferably from about 50 to about 300 milligrams per day. A soy yogurt is formulated having in a 170 gram serving about 8 grams of soy protein having about 8-24 milligrams of daidzein therein.
WO 00/45650 (International filing date Feb. 7, 2000, publication date xe2x80x9cCalcium Supplemented Food Products and Novel Calcium-Containing Ingredientxe2x80x9d and relates to foods and drinks and particularly to an emulsified fat spread which is supplemented with calcium. It is said that the spreads and other foods and drinks can be supplemented with vitamins, such as vitamins A and D, and with any other additives known to be beneficial to human health. Examples given include plant sterols or their esters to provide the additional benefit of cholesterol lowering, other vitamins and minerals, carotenoids (e.g., lycopenes), alpha tocopherol, antioxidants (e.g., ascorbic acid, flavonoids and isoflavones), lutein and other phytochemicals. In example 17, soy isoflavones are added to a spread. In claim 29, a food product or beverage is claimed having a food additive selected from the group consisting of vitamins, minerals, plant sterols, lycopenes, carotenoids, flavonoids, isoflavones, antioxidants, lutein and mixtures thereof. Proteins present in milk-derived solids are said to interact with nucleation sites or small crystals or particles of calcium salts to alter the normal course of crystallization or precipitation. It is said that proteins from other sources, eg., soya proteins or other plant-derived proteins and other food additives with one or more of the same functional groups, ie, carboxyl, hydroxyl, amino, amido, thiol or phenol groups when added to an aqueous solution prior to combining a calcium source with a source of anions should exert a similar influence on the organoleptic properties of the calcium composites when incorporated into emulsified fat spreads or other food and drink formulations.
WO 00/64276, published Nov. 2, 2000, is directed to spreads supplemented with isoflavones. It is said that phytosterols may also be added at up to 20 wt. %, especially up to 10 wt. % and that soy proteins may be added at between 0.4 wt. % and 2 or 3 wt. %. Priority from a US application is claimed.
WO 00/30665 published Jun. 2, 2000, discloses a composition comprising soy protein, a phytoestrogen compound and dietary fibers said to be useful to lower serum cholesterol and LDL cholesterol and serum triglycerides, and for increasing the HDL/LDL ratio. In claim 38 a composition further including a sterol is recited whereas in claim 39 a further compound which may be a stanol ester or a phytosterol is included. Various food products such as spreadable products, nutritional bars, liquids for drinking, etc. are mentioned.
WO 00/30663, published Jun. 2, 2000, discloses a composition comprising soy protein, a phytoestrogen compound and dietary fibers said to be useful to treat type 2 diabetes and cardiovascular diseases in a diabetic subject. The compositions can be used as a medicament and/or in the manufacture of a medicament. The composition can further include a sterol which may be a stanol ester or a phytosterol such as sitosterol. Various food products such as spreadable products, nutritional bars, liquids for drinking, etc. are mentioned. Alternatively, the invention provides a composition wherein no dietary fibres are present. Use in amounts effective in serum cholesterol levels and/or lowering LDL-cholesterol levels is mentioned.
WO 93/23069 discloses compositions enriched with phytoestrogens, or analogs, selected from genistein, daidzein, formononetin, and Biochanin A as a food additive, tablet or capsule for promoting health in cases of cancer, premenstrual syndrome or hypercholesterolaemia. Soy is among the many possible sources of phytoestrogens mentioned.
Setchell, et al. xe2x80x9cMammalian Lignans and Phyto-oestrogens Recent Studies on their Formation, Metabolism and Biological Role in Health and Disease,xe2x80x9d xe2x80x9cRole of the Gut Flora in Toxicity and Cancer,xe2x80x9d pp. 315-345 (1988), mentions interest in studies on the role of intestinal bacteria metabolism on hormones, bile acids and sterols.
Crank et al., U.S. Pat. No. 5,858,449 is directed to isoflavone-enriched soy protein products and methods for their manufacture. The product may be an ingredient in dairy or meat based food products such as infant formula, nutritional beverage, milk replacer, bologna, imitation processed cheese spread, water-injected ham, yogurt and frozen dessert. Crank et al., also discloses a method of making an isoflavone enriched soy product.
Example 5 discloses a soy based imitation processed cheese spread. Example 8 discloses a soy-based frozen dessert and a yogurt. The yogurt includes whey, vegetable oil, sugar, emulsifiers, salts, vitamins and minerals. The soybean products include daidzein, genistein, and glycitein.
Kelly, U.S. Pat. No. 5,830,807 is directed to compositions enriched with natural phytoestrogens or analogs thereof selected from genistein, daidzein, formononetin and biochanin A. It is said that they may be used as food additives, tablets or capsules for promoting health in cases of cancer, premenstrual syndrome, menopause or hyercholesterolaemia. Formulations may include drinks, solutions, syrups, etc.
WO 98/08503 discloses administration of an isoflavone-type compound used for various conditions including menopausal syndrome such as hot flashes, anxiety and depression, moods, swings, night sweats, headaches urinary incontinence, osteoporosis, premenstrual syndrome, fluid retention, cyclic mastalgia dysmenorrhea, Raynaud""s syndrome, Raynaud""s phenomenon and Buerger""s diseases, coronary artery spasms, migraine headaches, hypertension, benign prostatic hypertrophy, cancers of the breast, uterus, ovary, colon, endometrium, testicle, prostate, or large bowel, cyclical mastalgia, aeterosclerosis, Alzheimer""s disease, male impotency, inflammatory bowel syndrome, ulcerative colitis, Crohn""s disease, inflammatory effects such as rheumatoid diseases including rheumatoid arthritis acne, baldness, including male pattern baldness, psoriasis and diseases associated with oxidant stress including cancer, myocardial infarction, stroke, arthritis, sunlight induced skin damage or cataracts, and oxidant related disorders, inflammatory diseases, menopausal syndrome, anxiety, depression, mood swings, acne, estrogenic effects, androgenic effects, vasodilatory and spasmodic effects. It can be used with Vitamin E. Use as additives in foods and drinks such as health bars or desserts is mentioned.
The term xe2x80x9cfood stuffs,xe2x80x9d is said to be used in as wide as possible sense. It includes liquid formulations such as drinks, including dairy products, and other foods. Health drinks are mentioned.
Gorbach et al, U.S. Pat. No. 5,498,631 is directed to a method for treating symptoms of menopause, premenstrual syndrome or a condition resulting from reduced levels of indigenous estrogen by administering to the women an effective amount of an isoflavoid. Isoflavonoids which may be administered include genistein, daidzein, biochanin A, formononetin, o-desmethylangolensin and equol. The invention is said to feature a therapeutic dietary product for preventing or treating symptoms resulting from reduced or altered levels of indigenous estrogen. The dietary products preferably include a soy extract containing enriched isoflavonoids provided in a palatable food carrier, (e.g. a confectionery bar, biscuit, cereal or beverage).
WO 00/03684 discloses soy formulations comprising 3-23 milligrams of at least one isoflavone per gram, and which may also include 0.4 to 1.2 grams of protein per gram. The compositions may additionally include a medicinal composition such as drugs or prescription drugs utilized in estrogen replacement therapy, hormone replacement therapy, cholesterol lowering therapy, bone strengthening therapy, endometrial therapy, cancer therapy, Alzheimer""s therapy, ulcer therapy, prostrate therapy, skin therapy, renal therapy, blood therapy, lymphatic therapy, lung therapy, nervous system therapy, diabetes therapy, eye therapy and the like.
Jackson et al. U.S. Pat. No. 5,807,586 discloses a method of supplementing the dietary needs of women with many ingredients, including phytoestrogens.
Sekiya et al., U.S. Pat. No. 5,776,906 is directed to a method for promoting fat degradation comprising administrating to a human a composition containing an effective amount of an isoflavone, thereby promoting fat degradation in the fat cell. Soybean is mentioned as a potential source and daidzein, daidzein, genistein, genistin and derivatives thereof are mentioned. When the compositions intended to be a food it contains five to 1,000 milligrams-milliliter (g) of isoflavone.
Barnes et al., U.S. Pat. No. 5,506,211 discloses that the isoflavone genistein inhibits the acid secretion of osteoclasts and reduces bone resorption. The claims mention use of a genistein/glucoside conjugate. To reduce osteoclastic acid secretion one would generally contact one or more osteoclasts with a composition that comprises a biologically effective amount of genistein. Foodstuffs such as soy which contain genistein or concentrated forms thereof may be ingested to provide an animal with an effective amount of genistein. Various soy products such as soy protein may be used.
In human treatments, suitable methods include administering from 2 to 50 milligrams to 20 to 50 milligrams of genistein in the form of a food product. This may be achieved by ingesting between about 2 to 50 milligrams or about 20 to 50 milligrams of isolated soy protein per day per person. Barnes et al. acknowledge that genistein is known to be a tyrosine kinase inhibitor and has been proposed for use in treating several diseases and disorders, for example cardiovascular disease, atherosclerosis and certain cancers.
Jackson et al., U.S. Pat. No. 5,654,011 (Energetics) filed Jul. 30, 1996 is directed to a dietary supplement for supplementing the nutritional needs of pre-perimenopausal women.
Kelly, U.S. Pat. No. 5,830,887 is directed to compositions enriched with natural phytoestrogens selected from genistein, daidzein, formononetin and biochanin A. These may be used as food additives, tablets or capsules for promoting health in cases of cancer, premenstrual syndrome, menopause, or hyercholesterolaemia. In Example 4, soy hypocotyl was consumed as a powder added to the diet.
Liu et al., xe2x80x9cA comparison of pharmacodynamics between daidzein and a solid dispersion of daizeinxe2x80x9d, Shenyang Yaoxueyuan Xuebao, 1990, Vol. 7, No. 2, 123-5, pp 131 discloses that daidzein is used in clinical treatment of hypertension and coronary atherosclerotic heart disease, but is absorbed so slowly that is begins to show the effects only in a week""s time. A solid dispersion of daidzein is disclosed, and results are said to show that at equal dosage levels the solids dispersion produced more significant results on arrhythmia induced by BaCl2 in anesthetized rats.
Zilliken, U.S. Pat. No. 4,157,984 is directed to antioxidant compositions useful as stabilizers for food compositions including edible fats and oils. The compositions are prepared from a natural source, tempeh, a fermented soybean product. An ergostadientriol which possesses antioxidative properties and which in combination with mixtures of isoflavones provides compositions having exceptional antioxidative properties is disclosed. This can be used alone or in mixtures with isoflavones or other compounds.
Shlyankevich, U.S. Pat. No. 5,424,331 (Biovirus Research) is directed to a composition for treatment or prevention of osteoporosis which includes one or more phytoestrogen compounds, calcium contained in a biologically acceptable calcium salt, magnesium contained in a biologically acceptable magnesium salt, zinc contained in a biologically acceptable zinc salt, beta carotene, vitamin D and vitamin E. The compositions may be administered either as a dietary supplement or as a pharmaceutical.
WO 9610341 (Schouten Industries) discloses substantially pure hypocotyls of Glycine max which may be used in food and other products. They may be used as raw materials for isolation of isoflavones such as daidzin, genistin and glycitin. They may be incorporated in drinks, dairy products, bakery products, health teas and other products. In Example 2, a tomato juice cocktail is disclosed including tomato concentrate, green tea natural, beta carotene, natural vitamin E and Glycine max hypocotyl. The product contained 10 mg genistein/daidzein as glucosides per can of 163 ml.
Zilliken U.S. Pat. No. 4,390,559 is directed to isoflavones useful as antioxidants and useful in antioxidant compositions including edible fats and oils.
Schouten Industries, USA sells a soybean isolate product called SoyLife(copyright) comprising 40.5% protein, 11.2% fatty acid, 3.0% isoflavones, and 4.1% saponins. They suggest incorporating 1% to 5% of the SoyLife(copyright) product in any foods, including dietary drinks.
The present invention is directed to the discovery that three heretofore known classes of cholesterol lowering agents, soy protein, isoflavones (present within soy protein in nature), and phytosterols, when used in combination produce a greater cholesterol improvement effect than would be expected from data obtained from the use of fewer than all three together. It is contemplated that other vegetable proteins may be used in place of soy protein.
It has been discovered that a combined intervention with phytosterols and soy protein (including isoflavones) gives a clear synergistic hypocholesterolemic effect. Indeed, although the number of subjects tested thus far is insufficient for a rigorous confirmation of statistical significance, the combination has been found to have a greater-than-additive effect. Particularly in view of a previous (hamster) study conducted in a similar experimental conditions which demonstrated that by increasing dietary phytosterols supplementation from 0.24 to 0.48% (w/w) no extra hypocholestemic effect were achieved, the synergistic, indeed, greater than additive, cholesterol lowering effect of the combination of phytosterols and soy protein is surprising and can be expected to provide a useful tool in treating hypercholesterolemia in animals, particularly in humans.
While not wishing to be bound by theory, the action of the combined ingredients according to the invention might be related to different reported bioactivities between phytosterols and soy protein. It has been demonstrated that phytosterols inhibit intestinal cholesterol absorption, while soy proteins increase LDL receptor activity. Other studies have shown that soy protein increased hepatic cholesterol 7 alpha-hydroxylase activity, which enhances bile acid production. Therefore, from the additive action it can be presupposed that soy protein lowers blood cholesterol via increased removal of LDL from blood by increasing LDL-receptor activity and hepatic bile acid and cholesterol secretion into the intestines. This action is enhanced by phytosterols which inhibit cholesterol (re-)absorption from the intestines.
In addition to the cholesterol lowering effect, the combination significantly lowers blood triglyceride concentrations. This finding is in accordance with the hypotriglyceridemic effect of soy protein in human subjects as noted in the meta-analysis (Anderson et al.) mentioned above. Blood VLDL is the major carrier of blood TG in a fasting state. This suggests that the TG-suppressing effect of soy protein might be due to a suppressed VLDL production or metabolism. Since an increase of blood TG concentration has been assumed to be an independent risk factor for the development of cardiovascular disease, the combination of phytosterol with soy protein might have extra benefit in reducing the risk of cardiovascular disease.
While soy protein is a significant component of the inventive compositions, it is not believed that dietary fiber, e.g., soy fiber, contributes importantly. Therefore, the present compositions preferably include little or no soy or other dietary fiber. In particular, the compositions preferably include less than 4 wt %, especially less than 3 wt. % and more preferred less than 1 wt % or less of soy or other dietary fiber.
The compositions of the invention including the above described combination of cholesterol-lowering ingredients may take many forms, such as capsules, pills and gellcaps, but are especially foods such as, spreads, frozen desserts, beverages and nutritional bars.
Examples of preferred food products according to the invention are margarines or other spreads of oil based products, bakery products, dairy products, e.g. yogurt, cheese and milk-based drinks, beverages, e.g., soft drinks, fruit juices and tea and coffee based drinks, sauces, dressings and mayonnaise and confectionery products, e.g., frozen confectionery products such as water-ice or ice-cream. Especially preferred is the use in food products selected from the group of margarines and other spreads, tea based beverages, dressing and frozen confectionery products.
The spread is advantageously prepared by combining a fat phase with an aqueous phase, after which the mixture is processed into an emulsion and the isoflavones, soy protein and phytosterols and other additives are added.
For some foods, it will be possible to include the effective amounts of the ingredients in a single serving, whereas for others, it may be necessary to use multiple servings and/or combine servings of different foods. Keeping in mind, then, that it will not be possible with all foods to achieve the desired levels in a single serving, levels of the ingredients preferably used in accordance with the invention per serving are from 1 to 25 g soy or other vegetable protein (exclusive of any included isoflavone or phytosterol), from 5 to 150 mg isoflavone and from 0.2 to 3 g phytosterol. Especially preferred levels are from 1 to 8, or better from 3 to 7 g soy protein (exclusive of any included isoflavone or phytosterol), from 10 to 100 mg isoflavone and from 0.4 to 2.5 g phytosterol. Most preferred levels are from 5 to 6.5 g soy protein (exclusive of any included isoflavone or phytosterol), from 15 to 50 mg isoflavone and from 0.6 to 1.7 g phytosterol.
Depending on the intended consumer of the product, products of the invention may be supplemented with calcium, or, if desired, calcium supplementation can be omitted and/or calcium levels limited to provide a calcium-free or essentially calcium-free product. For instance the product may have less than about 1.5 wt. %, especially less than 0.5 wt. % or 0.1 wt. % total calcium salts (as salt) in the product. Most preferably, the products may have less than 0.5 wt %, especially less than 0.3 wt %, more preferably less than 0.1 wt % calcium based measured as calcium. Alternatively where calcium supplementation/higher levels or calcium are desired in the product, preferred calcium levels are given below. Where calcium is included, it is not generally necessary in accordance with the present invention to combine the individual constituents of the same calcium salts and precipitated in an aqueous solution of milk derived solids. Although the coprecipitation can generally be avoided, it may be useful in some situations. Where used, the calcium may be a soluble or an insoluble salt.
For a more complete understanding of the above and other features and advantages of the invention, reference should be made to the following detailed description of preferred embodiments and to the accompanying drawings.
Preferred sources of isoflavones include soy, clover, including red clover and subterranean clover, grains, chickpeas, ground nuts, lentils and beans, at levels of between 40 and 500 mg/100 g dry weight. Isoflavones are found in plants primarily bound to sugars such as glucose, as glycosides. Smaller amounts are found in plants in the aglucone form. The present invention encompasses addition of isoflavones in either bound and/or the free forms.
Soy may be used, for example, in the form of soybean flour; or the hull and/or hypocotyl may be used.
Processes for isolating phytoestrogens and phytoestrogen moiety-containing compounds and complexes from plants are well known. These include the process of Fluery et al. U.S. Pat. No. 5,141,746, the disclosure of which is incorporated by reference, Gugger et al. U.S. Pat. No. 5,702,752 and Shen et al. U.S. Pat. No. 5,637,562. Phytoestrogens are also available in the form of soy isoflavone concentrate obtained from soy flour and sold under the Soylife(copyright) trade name by Schouten USA, Inc. of Minneapolis, Minn. An additional source of phytoestrogens is Novasoy available from ADM.
Preferred levels of the phytoestrogens are at least 0.01 wt. % on the total weight of the product, which is preferably a food product, especially at least 0.05 wt. %.
By xe2x80x9cphytosterolsxe2x80x9d herein is meant plant sterols, esters of plant sterols, plant stanols or stanol esters and stanols and stanol esters derivable from plant sterols. Examples include sitosterol, sitostanol, their fatty acid esters, and the like. These may be included from 1 to about 20 wt. %, especially up to about 10 wt. % of the food product based on the sterol moiety.
More specifically, examples include alpha sitosterol, beta sitosterol, stigmasterol, ergosterol, campesterol, alpha sitostanol, beta sitostanol, campestanol and brassiciasterol. Although the foregoing are some of the more important phytosterols, at least 44 phytosterols have been identified and it will be apparent to one of ordinary skill that many of these will be appropriate for the present invention. Oryzanol may also be used. Phytosterols are identified in bean (1993) phytosterols in xe2x80x9cAdvance in Lipid Researchxe2x80x9d, pages 193-218, Paoletti, and Kiritchevsky, (Eds) Academic press, NY, the disclosure of which is incorporated herein by reference. The disclosure of xe2x80x9cEffect of Plant Sterols on Lipids and Atherosclerosisxe2x80x9d, Pollack, O. J., Pharmac, Ther., 31, 177-208 (1985) mentioned above is also incorporated by reference herein.
Among the more important sources are rice bran, corn bran, corn germ, wheat germ oil, corn oil, safflower oil, oat oil, olive oil, cotton seed oil, soybean oil, e.g., soybean oil distillates, peanut oil, black tea, orange juice, valencia, green tea, Colocsia, kale, broccoli, sesame seeds, shea oils, grapeseed oil, rapeseed oil, linseed oil, canola oil, tall oil from wood pulp and other resinous oil from wood pulp.
Soy protein can be obtained from numerous sources, including the Soylife(copyright) product mentioned above and Supro(copyright) from Dupont.
Spreads
A beneficial form for ingestion of isoflavones, soy protein and phytosterols is in the form of a water-in-oil spread, particularly a bread spread. It can be expected that the reported beneficial health effects of isoflavones, phytosterols and soy protein may be enjoyed by the consumer by consuming the spread without the need for pharmaceutical-type products, e.g., pills, capsules, etc. although these are within the invention as well.
In another preferred embodiment, the spread is an emulsion comprising added isoflavones, soy protein, phytosterols and at least 0.25 wt. % of a calcium salt, especially at least 0.5 wt. % of a calcium salt. The spread is preferably a water-in-oil emulsion. The spread is an excellent vehicle to provide women with the phytoestrogens and calcium both of which have enjoyed favorable reports concerning health effects.
In another preferred embodiment of the invention, the spread is an emulsion comprising isoflavones, soy protein, phytosterols and one or more, preferably at least two, of the following vitamins: A, D, E, B6 and B12. Preferably the spread also includes elevated levels of calcium and/or magnesium. Preferably this spread is also a water-in-oil emulsion.
Preferably a spread is provided with isoflavones, soy protein, phytosterols and a level and type of triglycerides such that at least 5 wt. % polyunsaturated fatty acid moieties are present (based on the total weight of the spread) to provide consumers with access to these substances in a beneficial food form. More preferably, the level and type of triglycerides is selected so that the spreads include at least 7 wt. %, especially up to a level of 20 wt. % polyunsaturated fatty acid moieties.
Isoflavones which may be used include genistein, daidzein, genistin, daidzin, equol, glycitein and glycitin.
Spreads according to the invention generally contain from less than 80% by weight of edible triglyceride materials. Suitable edible triglyceride materials are for example disclosed in Bailey""s Industrial Oil and Fat Products (1979). In higher fat spreads, the level of triglyceride material will generally be more than 60% and less than 80%, preferably from 70 to 79% by weight. In spreads of reduced fat content the level of triglycerides will generally be from 30-60%, more generally from 35 to 45% by weight. In very low fat spreads the level of triglycerides will generally be from 0 to 40%, for example, 30%, 25%, 20% or even 10% or about 0%.
Optional ingredients in the fat-continuous phase which is combined with the aqueous composition include emulsifiers, salt (particularly sodium chloride), preservatives, flavors, protein, vitamins, especially fat soluble vitamins such as vitamin A, antioxidants, antimicrobials, and preservatives, including citric and other acids. The emulsifiers can include mono- and diglycerides, polyglycerol esters, lecithin and polyoxyethylene sorbitan monoesters such as TWEEN 60 and TWEEN 80. One advantageous emulsifier is a polyglycerol polyricinoleate sold under the name Admul Wol available from Quest International, Naarden, the Netherlands.
Emulsifiers may be included at from 0.05 to 2% by weight, typically not more than 1% by weight.
It is preferred that the fat used is triglyceride fat derived from vegetable sources including soybean, canola, corn, sunflower, palm, Palm kernal, rapeseed, coconut, safflower, cottonseed, peanut and olive oils. Other digestible fat sources which may be used are fish oil, milk fat, skim milk fat, butterfat, lard and tallow. The oil will be hardened by hydrogenation if that is necessary to achieve the desired melting characteristics. Also, fractionation and interesterification may be used to obtain fats of the desire melting range. Especially preferred are fats having relatively large proportions of polyunsaturated fatty acid moieties, such as canola and soybean oils. The fat compositions mentioned in Netherlands patent documents No. NL 143115, NL 178559, NL 155436, NL 149687, NL 155177, and European patent documents EP 41303, EP 209176, EP 249282, and EP 470658, the disclosures of which are incorporated by reference, are highly suitable. If a fat blend is used it is most preferred that it comprises at least 30%, more preferably at least 45% of polyunsaturated fatty acid moieties, based on the total weight amount of the fat in the fat based food product to promote cholesterol lowering.
The fat can be a single fat or a blend. The use of a fat composition comprising a considerable amount of PUFA (polyunsaturated fatty acid) rich triglycerides is in particular considered highly beneficial.
Non-digestible fats may also be used as the fat source. Among the non-digestible fats are included polyol polyesters of C8 to C22 fatty acids such as sucrose polyester, sucrose polyethers, silicone oils/siloxanes, polycarboxylic acid esters, branched chain fatty acid triglycerides, neopentyl alcohol esters, dicarboxylic acid esters, jojoba oil and triglycerol ethers. Non-digestible fats may be used as from 0 to 100% of the fat, especially from 10 to 90%, and most especially from 25 to 75%.
Non-lipid fat replacers may also be used, to provide body to the product. These include protein-based fat replacers such as those described in Singer et al., U.S. Pat. No. 4,961,953 and cellulosic bulking agents such as microcrystalline cellulose and carboxymethyl cellulose.
Coloring agents, such as beta carotene, paprika, turmeric, annatto and yellow #5 and 6 and combinations thereof may be employed. The yellow color may desirably be used in combination with an opacifier like TiO2. It has been found that providing an appropriate color may be important since phytoestrogen sources such as soy flour impart a brownish color.
The soy protein which may be present in the compositions of the invention, may be present with the phytoestrogens which are added to the spread, as in soy flour.
Other vegetable proteins, such as peanut protein, cottonseed protein and the like may be used together with, or instead of, soy. In addition to soy proteins or other vegetable proteins, other proteins, if desired, can conveniently be included in the form of milk protein from whole, skim or other low fat milk and may comprise whey proteins (with or without lactose), acid casein and caseinates.
In addition to sodium chloride, flavor enhancers which may be employed include lactones, lipolyzed butter oils and started distillates, diacetyl, 2-octanone, butyric acid, hexanoic acid, and other fatty acids, esters of butyric acid, hexanoic acid, and other fatty acids, esters of butyric acid, delta-hydroxy acids and their glycerol esters and mixtures thereof.
Preservatives, such as benzoic acid, sorbic acid, phosphoric acid, lactic acid, acetic acid, hydrochloric acid and the soluble salts thereof may be used.
Antioxidants may include normal propyl gallagte, the tocopherols, including Vitamin E, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), nordihydorguaiaretic acid (NDGA), tertiary-butylhydroquinon (TBQH) and citric acid. Metal chelators or sequestrants such as sodium calcium salts of ethylenediamine tetra acetic acid (EDTA) may also be used.
Where the product takes the form of a water/oil emulsion, it will be appreciated that normally more hydrophobic additives will be added to the fat phase whereas more hydrophilic additives will normally be added to the aqueous phase.
The aqueous phase comprises water and, optionally other ingredients. A preferred ingredient is one or more gelling agents such as gelatin. Where the spread is a low fat spread, it is advantageous that the aqueous composition is gelled, which in some respects compensates for the lower amounts of fat in the product. It may be advantageous for the aqueous composition to be pre-gelled, i.e., gelled prior to combining the aqueous composition with the fat-continuous emulsion. Other suitable gelling agents include waxy maize starch such as Ultra-Tex 2, available from the National Starch and Chemical co., Bridgewater, N.J. or a rice starch such as Remyrise AC. A particularly effective combination of gelling agents has proved to be gelatin and waxy maize or rice starch. Other gelling agents include carrageenan, and a gelling hydrolyzed starch derivatives such as gelling maltodextrin, for example, Paselli maltodextrin SA2(copyright).
The amount of gelling agent may lie between 0 and 30%, mostly between 0.1 and 25% based on the weight of the aqueous phase of the spread. If hydrolyzed starches are present, their level may be from 2-20%; other gelling agents may be used at levels of up to 10%, mostly 1-7%, most preferred 2-5%, all of these percentages being based on the weight of the aqueous phase.
Hydrocolloids which are thickening rather than gelling agents may also be used. Hydrocolloids are described in Zeitschrift fur Lebenmittletechnologie und Verfahrenstechnk 32 (1981) 6, pp. 253-256. Hydrocolloids in addition to those mentioned above include polysaccharides such as native and modified starches, cellulose derivatives, pectins, galleon, xanthan gum, agar, Danish agar, furcelleran, gum arabic, guar gum, locust bean gum, algin, and alginates. Hydrocolloids will generally be used at levels of from 0.2 to 6%, based on total products. It will be appreciated that the gelling and thickening agents may be used in various combinations.
Additional ingredients which may be present in the aqueous phase include salt (particularly sodium chloride), preservatives, such as potassium sorbate, lactic and other acid, proteins, coloring agents, flavors, antimicrobials, antioxidants and vitamins, particularly water-soluble vitamins such as the B vitamins.
Addition of strong flavoring such as fruit purees, fruit flavors including vanilla and savory ingredients such as oregano and/or garlic, as well as spices and sugar can be important in masking off flour of phytoestrogen sources such as soy.
Proteins, water-soluble coloring agents, flavors, preservatives and antimicrobials and antioxidants useful in the aqueous composition are the same as those discussed above in connection with the fat phase, it being appreciated that generally the more hydrophilic additives are best placed in the aqueous phase.
A typical size for an average serving of spread or margarine is 14 grams. Preferred soy protein levels in the margarine or spread are 1 to 25 wt. %, more preferred 2 to 20 wt. %, especially preferred 4 to 20 wt. %, most preferred 4 to 15 wt. %. Preferred isoflavone levels in the margarine or spread are 0.003 to 1.7 wt. %, more preferred 0.07 to 0.71 wt. %, especially preferred 0.11 to 0.36 wt. %, most preferred 0.07 to 0.13 wt. %. Preferred phytosterol levels in the margarine or spread are 0.65 to 21 wt. %, more preferred 3 to 18 wt. %, especially preferred 4 to 12 wt. %, most preferred 5 to 10 wt. %. Preferred calcium levels in the margarine or spread are 0.3 to 7 wt. %, more preferred 0.33 to 3.5 wt. %, especially preferred 0.35 to 1.75 wt. %, most preferred 0.35 to 0.7 wt. %.
Although melatonin may be added, compositions in which melatonin is essentially not present, especially compositions in which melatonin is completely absent, are preferred.
The balance of the spread is largely water, which may be incorporated at levels of up to 99.9% by weight, more generally from 10 to 98%, preferably from 20 to 97% by weight. Spreads according to the invention may be fat- or water-continuous, preferably fat-continuous.
Frozen Confectionery Products
For the purpose of the invention the term frozen confectionery product includes milk containing frozen confections such as ice-cream, frozen yoghurt, sherbet, sorbet, ice milk and frozen custard, water-ices, granitas and frozen fruit purees.
Preferably the level of solids in the frozen confection (e.g. sugar, fat, flavouring etc) is more than 3 wt. %, more preferred from 10 to 70 wt, for example 40 to 70 wt. %.
Ice-cream will typically comprise 2 to 20 wt. % of fat, 0 to 20 wt. % of sweeteners, 2 to 20 wt. % of non-fat milk components and optional components such as emulsifiers, stabilizers, preservatives, flavoring ingredients, vitamins, minerals, etc, the balance being water. Typically ice-cream will be aerated e.g. to an overrun of 20 to 400%, more generally 40 to 200% and frozen to a temperature of from xe2x88x922 to xe2x88x92200 C, more generally xe2x88x9210 to xe2x88x9230 C. Ice-cream normally comprises calcium at a level of about 0.1 wt. %.
A typical size of an average serving of frozen confectionery material is 66 grams. Preferred soy protein levels in the frozen confectionery are 0.7 to 25 wt. %, more preferred 0.7 to 15 wt. %, especially preferred 1.6 to 12.0 wt. %, most preferred 3 to 9 wt. %. Preferred isoflavone levels in the frozen confectionery are 0.0015 to 0.3 wt. %, more preferred 0.03 to 0.20 wt. %, especially preferred 0.02 to 0.17 wt. %, most preferred 0.008 to 0.09 wt. %. Preferred phytosterol levels in the frozen confectionery are 0.3 to 7.0 wt. %, more preferred 0.3 to 6.0 wt. %, especially preferred 0.6 to 5.0 wt. %, most preferred 0.6 to 3.0 wt. %. Preferred calcium levels are 0.15 to 3 wt. %, more preferred 0.17 to 1.5 wt. %, especially preferred 0.18 to 0.75 wt. %, most preferred 0.18 to 0.3 wt. %.
Tea Based Products
For the purpose of this invention the term tea based products refers to products containing tea or tea replacing herbal compositions e.g. tea-bags, leaf tea, herbal tea bags, herbal infusions, powdered tea, powdered herbal tea, ice-tea, ice herbal tea, carbonated ice tea, carbonated herbal infusions etc.
Typically some tea based products of the invention may need a preparation step shortly before consuming, e.g. the making of tea brew from tea-bags, leaf tea, herbal tea bags or herbal infusions or the solubilization of powdered tea or powdered herbal tea. For these products it is preferred to adjust the level of isoflavones, soy protein, phytosterol and optionally calcium in the product such that one serving of the final product to be consumed has the desired levels of isoflavones, soy protein and phytosterol as described above.
For ice-tea, ice herbal tea, carbonated ice tea, carbonated herbal infusions the typical size of one serving will be 250 ml or 250 grams. Preferred levels of soy protein in these ready-to-drink products are 0.4 to 10 wt. %, more preferred, 1.2 to 8 wt. %, especially preferred 2 to 6 wt. %, most preferred, 2 to 4 wt. %. Preferred levels of isoflavone in these ready-to-drink products are 0.0004 to 0.1 wt. %, more preferred, 0.0008 to 0.05 wt. %, especially preferred 0.0016 to 0.016 wt. %, most preferred, 0.002 to 0.02 wt. %. Preferred levels of phytosterols in these ready-to-drink products are 0.08 to 1.5 wt. %, more preferred, 0.16 to 1 wt. %, especially preferred 0.2 to 0.8 wt. %, most preferred, 0.24 to 0.7 wt. %. Preferred levels of calcium in these ready to drink products are 0.04 to 0.8 wt. %, more preferred, 0.045 to 0.4 wt. %, especially preferred 0.05 to 0.2 wt. %, most preferred, 0.05 to 0.08 wt. %.
For products which are extracted to obtain the final product, generally the aim is to ensure that one serving of 250 ml or 250 grams comprises the desired amounts as indicated above. In this context it should be appreciated than normally only part of the isoflavones present in the tea based product to be extracted will eventually be extracted into the final tea drink. To compensate for this effect generally it is desirable to incorporate into the products to be extracted about 2 times the amount of isoflavones as is desired to have in the extract.
Salad Dressings or Mayonnaise
Generally dressings or mayonnaise are oil in water emulsions. The oil phase of the emulsion generally is 0 to 80 wt. % of the product. For non fat reduced products the level of fat is typically from 60 to 80%, for salad dressings the level of fat is generally 10-60 wt. %, more preferred 15-40 wt. % Low or no fat dressings may for example contain triglyceride levels of 0, 5, 10, 15% by weight.
Dressings and mayonnaise are generally low pH products having a preferred pH of from 2-6.
Dressings or mayonnaise optionally may contain other ingredients such as emulsifiers (for example egg-yolk), stabilizers, acidifiers, biopolymers, bulking agents, flavors, coloring agents etc. The balance of the composition is water which could advantageously be present at a level of 0.1 to 99.9 wt. %, more general 20-99 wt. %, most preferred 50 to 98 wt. %.
A typical size for an average serving of dressings is 30 and mayonnaise is 14 grams. Preferred soy protein levels in the dressings or mayonnaise are 1 to 25 wt. %, more preferred 2 to 20 wt. %, especially preferred 4 to 20 wt. %, most preferred 4 to 15 wt. %. Preferred isoflavone levels in the dressing or mayonnaise are 0.003 to 1.0 wt. %, more preferred 0.07 to 0.67 wt. %, especially preferred 0.10 to 0.33 wt. %, most preferred 0.05 to 0.017 wt. %. Preferred phytosterol levels in the dressings or mayonnaise are 1 to 20 wt. %, more preferred 3 to 17 wt. %, especially preferred 4 to 11 wt. %, most preferred 2 to 6.0 wt. %. Preferred calcium levels in the margarine or spread are 0.3 to 7 wt. %, more preferred 0.33 to 3.5 wt. %, especially preferred 0.35 to 1.75 wt. %, most preferred 0.35 to 0.7 wt. %.

Composition for lowering blood cholesterol